| AN APPROACH TO THE REACTION MECHANISM OF GEM-DIHALOCYCLOPROPANES WITH METALS UNDER ULTRASONIC IRRADIATION |
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| 作者姓名： | 许临晓 于同隐 陶凤岗 吴世晖 |
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| 作者单位： | Institute of Material Science，Fudan University，Shanghai，Institute of Material Science，Fudan University，Shanghai，Department of Chemistry，Fudan University，Shanghai，Department of Chemistry，Fudan University，Shanghai |
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| 基金项目： | Project supported by the National Natural Science Foundation of China. |
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| 摘 要： | The reactive intermediate cyclopropylidene, generated quickly by the reactions of dihalocyclopropanes with lithium or magnesium under ultrasonic irradiation, can be trapped by olefins and the corresponding spriopentane derivatives are obtained, Based on the identification of the intermediate and the products of the reaction, a mechanism is proposed that the radical intermediate should be generated at first via a single electron transfer process, sequentially it gains another electron from the metals to form the carbenoid intermediate which then leads to the main products by insertion, addition or rearrangement. On the other hand, it can also abstract the hydrogen atom from the solvent to form the corresponding monohalide which then converts into the cyclopropane derivatives. Discussions on and verifications for the reaction mechanism are given in this paper.
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AN APPROACH TO THE REACTION MECHANISM OF GEM-DIHALOCYCLOPROPANES WITH METALS UNDER ULTRASONIC IRRADIATION |
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| XU LINXIAO YU TONGYIN.AN APPROACH TO THE REACTION MECHANISM OF GEM-DIHALOCYCLOPROPANES WITH METALS UNDER ULTRASONIC IRRADIATION[J].Science in China(Chemistry),1988(8). |
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| Authors: | XU LINXIAO YU TONGYIN |
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| Abstract: | The reactive intermediate cyclopropylidene, generated quickly by the reactions of dihalocyclopropanes with lithium or magnesium under ultrasonic irradiation, can be trapped by olefins and the corresponding spriopentane derivatives are obtained, Based on the identification of the intermediate and the products of the reaction, a mechanism is proposed that the radical intermediate should be generated at first via a single electron transfer process, sequentially it gains another electron from the metals to form the carbenoid intermediate which then leads to the main products by insertion, addition or rearrangement. On the other hand, it can also abstract the hydrogen atom from the solvent to form the corresponding monohalide which then converts into the cyclopropane derivatives. Discussions on and verifications for the reaction mechanism are given in this paper. |
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| Keywords: | cyclopropylidene free radical ultrasound reaction mechanism |
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